Mineral fortification of foodstuffs



PatentedMar. 13,1945

' UNITED STATES PATENT OFFICE 2,371,189 I J MINERAL FORTIFIOATION orroons'rurrs Delaware No Drawing. Application July 2, 1943, v

I Serial No. 493,253-

12 Claims. .(Ol. 99-83) The present invention relates to the mineralfortification of foodstuffs such as flour, cereals, and edible cerealproducts with salts of anacardic acid and tetrahydroanacardic acid andmore particularly to the fortification with the copper,

manganese and iron salts of these acids. The principal object of myinvention is to increase the copper, .iron and/or manganese content offoodstuffs by the, addition thereto of colorless, non-ionizing compoundsof anacardic ac'd and tetrahydroanacardic' acid, said compounds beingnon-ionizing in water, and insolublev in water and in dilute acids.

Another object or my invention is'to restore the naturally occurringmineral constituents of whole cereal grains to milled or refinedflourand other edible cereal products so that the .iinal product willhave'approximately the same mineral content as that of the product priorto refining or milling.

A further object of my invention is the provision of a method ofinclusion in foodstuffs of non-ionized iron, manganese and coppercompounds of anacardic acid and tetrahydroana cardic acid, and whichbecause of their nonionization, under normal conditions, donot lac--vcelerate the development of rancidity in such foodstuifs.

A still further object of my invention is to provide assimilablemineral-fortified food compounds containin'g non-ionizing salts ofanacardic acid andtetrahydroanacardic acid which are capable oipreventing or correcting mineral de ficiencies in animals when includedin the diet of such animals.

In the milling oi. flour and other cereal products. a major portion ofthenaturally occurring mineral constituents'such as iron, copper,mansanese and calcium salts, are removed in the relining or millingoperation and are found in the color to the flour which renders theflour undesirable for commercial purposes. Also, ferric chloridesolution has been applied to flour but ample, when flour is to betreated, the powdered the above-mentioned disadvantages may be obviatedby incorporating a suitable amount 0! a non-ionized appropriate salt oranacardic acid or tetrahydroanacardic acid which is insoluble in waterand in dilute acids into the flour or" other foodstuff. These salts maybe incorporated inthe foodstufl' in any desired manner. For exsalt isblended with the flour by suitable mixing therewith, in a proportion ofabout 1 to 5 parts of the salt to about 1,000 parts oi flour. Ifdesired, a colloidal suspension of the salt of anacardic acid ortetrahydroanacardic acidmay-be sprayed on an edible cereal product. I

In practicing my invention, I first prepare a suitable salt of anacardicacid or of tetrahydroanacardic acid. For example, if a suitable neutralor basic ferrous or ferric anacardate is desired it may beprepared asfollows:

Basic ferrous anacardate-FezAm A solution of disodium anacardate wasmade by dissolving 50 grams of anacardic acid in one liter of Watercontaining 11.5 grams of sodium hydroxide. To this was added a solutionof 38.8

grams of ferrous sulfate (FeSO-r'II-hO) dissolved in a small amount oiwater. The precipitate was collected on a filter, washed, dried, and comminuted. e

A ferrous sodium tetrahydroanacardate may be prepared as described aboveexcept that the ana cardic acidis first converted into tetrahydroanncardic acid by hydrcgenating anacardic acid in the presence of asuitable catalyst at an elevated temperature by conventional procedure.

Neutral ferrous anatardata-Fedm A solution of sodium anacardate was madeby dissolving 50 grams of anacardic acid in one liter of watercontaining 5.8 grams of sodium hydroxide. grams of ferrous sulfate(FeSOUIHzO) dissolved in a small amount oi water. The precipitate wasextracted with ether. The ether was removed and the residue taken up inhexane and the hexane was removed by distillation.

. above.

since it is highly ionized. it accelerates the development of ranolditvin the flour and it also imparts an objectionable color to the flour. Myinvention is based upon the discovery that A neutral ferroustetrahydroanacardate' may be prepared by first converting the anacardicacid into tetrahydroanacardic acid, as described above, and thenfollowing the procedure outlined Basic ferric cnacardateFeAm A solutionof disodium anacardate was prepared by dissolving 50 grams of anacardicacid in one liter of water containing 11.5 grams of To this was added asolution 01' 19.4

A solution of sodium anacardate was prepared by dissolving 50 grams ofanacardic acid in one liter of water containing 5.8 grams of sodiumhydroxide. To this was added a solution of 7.5 grams of ferric chloridein a small amount of water. A precipitate was formed which was separatedby-means of hexane. Distillation of the hexane removed the water fromthe material and complete removal of the hexane left a solid salt.

A neutral ferric tetrahydroanacardate may be prepared by firstconverting anacardic acid into tetrahydroanacardic acid, as describedabove, and then following the procedure outlined above.

A neutral and a basic copper anacardate, which may be utilized accordingto the present inven tion, may be prepared as follows:

Basic copper anacardatee-C'uAn A solution of disodium anacardate wasmade by dissolving 50 grams of anacardic acid in one liter of watercontaining 11.5 grams of sodium hydroxide dissolved in a small amount ofwater. To this was added a solution of 23.8 grams of copper chloride(CuCh.2HzO) The solid precipitate thus formed was collected on a filter.washed and dried.

Neutral copper anacardate-CuAnZ A solution of sodium anacardate wasprepared by dissolving 400 grams of 90% anacardic acid in about twoliters of water containing 42.8 grams of sodium hydroxide. To thissolution was added a solution of 89.2 grams of cupric chloride dissolvedin about 300 c. c. of water. A brownish-green oil latter solution wascooled to about 40' C. and a solution of 1.43 grams of cupric acetatemonohydrate in two hundred milliliters of water was added slowly witheffective agitation. The resulting precipitate was collected on afilter, washed, and dried in air, yielding 11.2 grams of a solid havinga melting point of 82 to 84 C.

Copper tetrahydroanacardatwllasic present invention, may be prepared asfollows;

precipitated partially in emulsified form. Ether was added, the layersseparated. and the ether solution of the copper anacardate was washedwith water. dried with sodium sulfate and concentrate by distillation.

Neutral copper anacardate-Alternative procedure Copper hydroxide wasprepared by adding a soiution of 22.8 grams of sodium hydroxide in about200 c. c. of water to a solution of 48.4 grams of cupric chloride inabout 300 c. c. of water.- The resulting precipitate of copper hydroxidewas col- I lected on a filter and washed thoroughly with f C ppertetrahudroanacardate-Neutral Ten grams of tetrahydroanacardic acid weredissolved in three hundred milliliters of hot water containing 0.5? gramof sodium hydroxide. The

Basic manganese anacardate-MnAn A solution of disodium anacardate wasprepared by dissolving 50 grams of anacardic acid in one liter of watercontaining 11.5 grams of sodium hydroxide. To this was added a solutionof 17.3 grams of manganous chloride (MnClz) dissolved in a small amountof water. The precipitate which formed was collected on a filter,washed.

and dried.

Neutral manganese anacardateMnAm A solution of sodium anacardate wasprepared by dissolving 50 grams of anacardic acid in one liter of watercontaining 5.8 grams of sodium hydroxide. To this was added a solutionof 8.7 grams of manganous chloride dissolved in a small amount of water.The precipitate which formed was collected on a filter, washed, anddried.

The following neutral and basic manganese tetrahydroanacardates may beprepared and utilized according to the present invention:

Neutral manganese tetrahydroanacardate Five grams of tetrahydroanacardicacid were dissolved in about three hundred milliliters of hot watercontaining 0.57 gram of sodium hydroxide, and the solution was cooled toabout 40 C. To this solution was added with eflective stirring asolution of 1.42 grams of manganous chloride tetrahydrate dissolved inabout 100 milliliters of water. The resulting precipitate was collectedon a filter and dried in air, yielding 5.55 grams of a solid melting at142 to 147 C.

Basic manganese tctrahydroanacardate Five grams of tetrahydroanacardicacid were I dissolved in about three hundred milliliters of hotpreferred relative proportions: 004% to 2%, by

weight, of the salt, or .004 lb. to 2 lbs. per pounds of flour, or otherfood.

While iron, copper, and manganese anacardates andtetrahydroanacardateshave been specifically mentioned above, it will be understood that otherfood which will correct anemic conditions.

It will, of course, be understoodthat the abovementioned anacardatesalts are substantially colorless, tasteless, and odorless andrelatively non-hygroscopic and. stable on storage. Therefore, one ormore of these salts may be mixed or incorporated with flour orothercereal products during or after the milling-thereof and the treated.product will retain its original composition unimpaired.

Tannins occur in practically all natural food products and would give,with ionized iron, definite ink-like discoloration. Inks are quitefrequently made by the use of ferric salts and tannic acid. However, Ihave found that my non-ionized copper, iron, and manganese anacardatesand tetrahydroanacardates do not react with tannic acid under normalconditions. No discoloration occurs in food products which containtannin,

when iron, copper, and. manganese anacardates and tetrahydroanacardatesare added to them,

By the term "cereal products" as used, in this specification andin theclaims, I mean a product derived wholly or substantially fromcereal-grains or products derived from the milling thereof. As iexamples of these products, I may cite malted fiours, farina, doughnutflour, bread and cake flours, breakfast cereals, pancake and biscuitfiours;

The foregoing specification and description include the essential anddistinctive thought of my invention, but it is to be distinctlyunderstood that the same-may be modified in various ways and/ orcombined withv'arious other details without affecting .the peculiarresults obtained,and without departing from the spirit of the inventionor herent in my invention.

I claim as my invention:

1. The method of fortifying edible flour and breakfast cereal withminerals which consists in blendinfl a non-ionized salt of anacardicacid selected from the group consisting of copper, iron,

the scope of the appended claims in which. I intend to claim allthepatentable noveltyinof copper, iron, and manganesetetrahydroanacardates, with the refined product in such pro-' portion asto restore to the product approximately the mineral content thereofwhich existed prior to the refining thereof.

3. The method of fortlfying edible fiour and breakfast cereal with ironwhich comprises blending a non-ionized iron anacardate' salt with therefined product in such proportion as to restore to the productsubstantially the iron content thereof which existed prior to therefining of the product.

4. Themethod of fortifying edible flour and breakfast cereal withironwhich comprises blend-' ing a non-ionized iron tetrahy'droanacardatesalt with the refined product in such proportion as to restore to theproduct substantially the iron content thereof which existed prior tothe refining of the product. 7 1

5. The method of fortifying edible flour and breakfast cereal with.manganese which comprises blending a non-ionized manganesetetrahydroanacardate salt with the refined product in such proportion asto restore to the product substantially the manganese content thereofwhich existed prior to the refining of the product.

6. An edible solid mixture of a mineral fortified cereal productconsisting of such a product blended with a non-ionized salt ofanacardic acid selected fromthe group consisting of copper, iron, andmanganese anacardates. v

'7. Anedible solid mixture of amineral fortified cereal productconsisting of such a product blended with a non-ionized salt oftetrahydroanacardic acid selected from the group consisting of copper,iron, and manganese tetrahydroanacardates.

8. An ediblemineral fortified flour consisting of refined flour blendedwith a non-ionized iron 'anacardate salt.

9. An edible mineral fortified fiour'consistins of refined flour blendedwith a non-ionized iron tetrahydroanacardate salt.

10. An edible mineral fortified flour consisting of refined fiourblendedwith a non-ionized manganese tetrahydroanacardate salt.

11. The method of fortifying edible fiourand breakfast cereal withminerals which comprises blending a non-ionized salt of an acid selectedfrom the group consisting of anacardic acid and tetrahydroanacardic acidand metal selected from the group consisting of copper, iron, and

and manganese -anac'ardates, with the: edible product in such proportionas to restore to the product approximately the mineral content thereofwhich existed prior to the refinin thereof.

2. The method of fortifying refined edible flour and breakfast cerealwith minerals which con-- sists inblending a non-ionized salt oftetrahydroanacardic acid selected from the group consisting manganesewith the edible product in such proportions as to restore to the productapproximately the mineral content thereof which existed prior to therefining thereof. I

12. An edible solid mixture Of 9' mineral fortified cereal productconsisting of such a product blended with a non-ionized-salt of an acidselected from the group consisting of anacardic acid andtetrahydroanacardic acid and a metal selected from the group of copper,iron,

and manganese.

' ROBERT E. SADTLER-

